Elmhurst police said a Chevrolet SUV, driven by a woman, was traveling east on St. Charles Road near Hill Avenue just after 5 a.m. when it drifted over the center line and hit an Audi SUV traveling west head-on.
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When Elmhurst police and fire crews arrived, they transported the woman driver and sole occupant of the Audi to Elmhurst Hospital with serious injuries.
The driver of the Chevrolet was extricated from the vehicle, but had already died, police said.
She has not yet been publicly identified.
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A 4-year-old boy and 2-year-old girl were also extricated from the Chevrolet and taken to Loyola University Medical Center with serious injuries, police said.
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Officials said the two vehicles had significant front-end damage.
The roadway was closed until about 11:30 a.m., while police investigated.
Anyone with information is asked to call Elmhurst police at (630) 530-3050.